It is known that certain water-soluble phthalocyanine, naphthalocyanine, and metallocyanine compounds can be used as photobleaching and anti-microbial agents. Phthalocyanines and naphthalocyanines or their metal complexes can form "singlet oxygen" an oxidative species capable of reacting with stains to bleach them to a colorless and usually water-soluble state.
There are many examples of phthalocyanines and naphthalocyanines photobleaches, the most common being the zinc and aluminum phthalocyanines. In the literature the term "photosensitizer" is often used instead of "photoactivator" and may therefore be considered as standing equally well for the latter term used throughout this specification.
The prior art teaches phthalocyanine and naphthalocyanine compounds having the general structure ##STR1##
where Me is a transition or non-transition metal, (Sens.) is a phthalocyanine or naphthalocyanine ring which, when combined with a suitable Me unit, is capable of undergoing photosensitization of oxygen molecules, R units are substituent groups which are bonded to the photosensitization ring units (Sens.) to enhance the solubility or photochemical properties of the molecule, and Y units are substituents associated with the metal atom, for example, anions to provide electronic neutrality. The selection of a particular substituent R unit for substitution into the molecule has been the focus of many years of research and these units are typically chosen by the formulator to impart into the target molecule the desired level of water solubility. PA1 wherein P is a photosensitizing unit; each D is independently a unit having the formula: EQU --L.sup.1 --R PA1 a) a photosensitizing group; PA1 b) a photoactive metal or non-metal chelated by said photosensitizing group; PA1 c) at least one photochemical mediating axial moiety bonded to said photoactive metal or non-metal, said photochemical mediating axial moiety comprises at least one heavy atom within ten covalent bonds of the point of attachment of said photochemical mediating axial moiety to said photoactive metal or non-metal, said heavy atom selected from the group consisting of chlorine, bromine, iodine, and mixtures thereof; and PA1 d) one or more axial moieties which mediate the solubility or substantivity of the singlet oxygen generator molecule, said solubility or substantivity mediating axial moiety is bonded directly to said photoactive metal or non-metal, or to the photochemical mediating axial moiety at the end distal to the photosensitizing group. PA1 wherein R.sup.13 and R.sup.14 are independently selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkenyl, C.sub.1 -C.sub.6 alkoxy, C.sub.3 -C.sub.6 branched alkoxy, halogen, morpholino, cyano, nitrilo, --CO.sub.2.sup.- M.sup.+, --SO.sub.3.sup.- M.sup.+, --OSO.sub.3.sup.- M.sup.+, --N(R.sup.15).sub.2, and --N.sup.+ (R.sup.15).sub.3 X.sup.- wherein each R.sup.15 is independently hydrogen or C.sub.1 -C.sub.4 alkyl; and mixtures thereof; wherein M is a water soluble cation and X is chlorine, bromine, iodine, or other water soluble anion. Examples of other water soluble anions include organic species such as fumarate, tartrate, oxalate and the like, inorganic species include sulfate, hydrogen sulfate, phosphate and the like. PA1 wherein R.sup.13 and R.sup.14 are the same as define above, p is from 1 to about 10. PA1 wherein R.sup.13 and R.sup.14 are the same as define above. PA1 wherein R.sup.13 and R.sup.14 are the same as define above, q is from 0 to about 10. PA1 wherein R.sup.13 and R.sup.14 are the same as define above, w is from 1 to about 10. PA1 wherein R.sup.10, and R.sup.11 are each a C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, R.sup.12 is hydrogen, C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl and mixtures thereof, A is the heteroatom nitrogen or oxygen, preferably A is oxygen, the index v is 0 when the heteroatom is absent, v is equal to 1 when the heteroatom is present, X is chloride, bromide, iodide, or other water soluble anion, u is from 0 to 22. Examples of other water soluble anions include organic species such as fumarate, tartrate, oxalate and the like, inorganic species include sulfate, hydrogen sulfate, phosphate and the like. PA1 wherein R.sup.16 is C.sub.1 -C.sub.4 alkyl, chlorine, bromine, or iodine; the index i has the value from 1 to 18, the index j has the value from 1 to 18, and the value of i+j can not exceed 20. When the C.sub.1 -C.sub.20 linear or branched alkylene moieties comprise photochemical mediating axial moieties the heavy atoms chlorine, bromine, and iodine must be substituted at a carbon atom within ten covalent bonds of the proximal end of the alkylene moiety, said proximal end is connected to the photoactive metal or non-metal. PA1 wherein R.sup.6 is hydrogen, C.sub.1 -C.sub.4 alkyl, chlorine, bromine, iodine, and mixtures thereof. When the C.sub.1 -C.sub.20 substituted or unsubstituted arylene moieties comprise photochemical mediating axial moieties the heavy atoms chlorine, bromine, and iodine must be substituted at a carbon atom within ten covalent bonds of the proximal end of the arylene moiety, said proximal end is connected to the photoactive metal or non-metal. PA1 wherein R.sup.16 is hydrogen, C.sub.1 -C.sub.4 alkyl, chlorine, bromine, iodine, and mixtures thereof, the index p has the value from 1 to 24. When the C.sub.7 -C.sub.30 substituted or unsubstituted alkylenearylene moieties comprise photochemical mediating axial moieties the heavy atoms chlorine, bromine, and iodine must be substituted at a carbon atom within ten covalent bonds of the proximal end of the alkylenearlyene moiety, said proximal end is connected to the photoactive metal or non-metal. PA1 wherein R.sup.16 is hydrogen, C.sub.1 -C.sub.4 alkyl, chlorine, bromine, iodine, and mixtures thereof. When the C.sub.6 -C.sub.20 substituted and unsubstituted aryleneoxy moieties comprise photochemical mediating axial moieties the heavy atoms chlorine, bromine, and iodine must be substituted at a carbon atom within ten covalent bonds of the proximal end of the aryleneoxy moiety, said proximal end is connected to the photoactive metal or non-metal. PA1 wherein rings A, B, C, and D are aromatic rings independently selected from the group consisting of substituted and unsubstituted benzene, substituted and unsubstituted naphthalene, substituted and unsubstituted anthracene; substituted and unsubstituted phenanthrene, and mixtures thereof. PA1 wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently selected from the substituents described herein below. PA1 wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are independently selected from the substituents described herein below. PA1 wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 units are independently selected from the substituents listed herein below. PA1 wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 units are independently selected from the substituents described herein below. PA1 wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 units are independently selected from the substituents described herein below. PA1 wherein Z is hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkyl, C.sub.1 -C.sub.30 alkoxy, --CO.sub.2 H, --OCH.sub.2 CO.sub.2 H, --SO.sub.3.sup.- M.sup.+, --OSO.sub.3.sup.- M.sup.+, --PO.sub.3.sup.2- M, --OPO.sub.3.sup.2- M, or mixtures thereof; M is a water soluble cation in sufficient amount to satisfy charge balance; x is 0 or 1, each y independently has the value from 0 to 6, each z independently has the value from 0 to 100; PA1 i) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof; PA1 ii) halogen substituted C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof; PA1 iii) polyhydroxyl substituted C.sub.3 -C.sub.22 alkylene; PA1 iv) C.sub.3 -C.sub.22 glycol; PA1 v) C.sub.1 -C.sub.22 alkoxy; PA1 vi) C.sub.3 -C.sub.22 branched alkoxy; PA1 vii) substituted aryl, unsubstituted aryl, or mixtures thereof; PA1 viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; PA1 ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; PA1 x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; PA1 xi) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof; PA1 R.sup.10 and R.sup.11 are C.sub.1 -C.sub.2 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof; PA1 R.sup.12 is: PA1 A is nitrogen or oxygen; X is chlorine, bromine, iodine, or other water soluble anion, v is 0 or 1, u is from 0 to 22; PA1 wherein R.sup.17 and R.sup.18 are C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof; PA1 wherein Z is: PA1 A is nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to 12; PA1 wherein each R.sub.19, R.sup.20, and R.sup.21 is independently PA1 wherein the R.sup.1, R.sup.2, R.sup.3, and R.sup.4 units of each benzene ring is a hydrogen atom. PA1 wherein the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 units of each naphthylene ring is a hydrogen atom. PA1 wherein the R.sup.1, R.sup.2, R.sup.3, and R.sup.4 units of each of the benzene rings is a hydrogen atom, and the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 units of the naphthylene ring is a hydrogen atom. PA1 wherein the ratio of the indices x and y indicate the stoichiometric amounts of each reacant, said reactant ratios can range from 0.01 to 100, that is the value of x can be 1 when the value of y is 100 and the value of x can be 100 when the value of y is 1. For example, the following formula ##STR26## PA1 is a major product from the following reaction stoichiometry ##STR27## PA1 wherein R' is aryl, substituted aryl, and mixtures thereof, as defined herein above. PA1 wherein L.sup.1 is C.sub.1 -C.sub.20 linear or branched alkylene, C.sub.1 -C.sub.20 linear or branched alkenylene, C.sub.6 -C.sub.20 substituted or unsubstituted arylene, C.sub.6 -C.sub.20 substituted or unsubstituted aryleneoxy, C.sub.7 -C.sub.30 linear or branched alkylarylene, provided L.sup.1 is substituted within 10 covalent bonds of the photoactive metal or non-metal M by at least one heavy atom, said heavy atom selected from the group consisting of chlorine, bromine, iodine, and mixtures thereof. Each D unit is covalently bonded at its proximal end to a photoactive metal or non-metal, said metal or non-metal chelated by the photosensitizing group. The distal end of the moiety D is comprised of an R unit, therefore each L.sup.1 unit is bonded at its distal end to an R unit which is further defined herein below. D units serve as a tether thereby placing the heavy atoms of the photochemical mediating moiety in a position proximal to the photosensitizing group wherein the heavy atoms can interact with the photosensitizing group. PA1 wherein Z is hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkyl, C.sub.1 -C.sub.30 alkoxy, --CO.sub.2 H, --OCH.sub.2 CO.sub.2 H, --SO.sub.3.sup.- M.sup.+, --OSO.sub.3.sup.- M.sup.+, --PO.sub.3.sup.2- M, --OPO.sub.3.sup.2- M, and mixtures thereof; M is a water soluble cation in sufficient amount to satisfy charge balance; x is 0 or 1, each y independently has the value from 0 to 6, preferably from 0 to 6; each z independently has the value from 0 to 100, preferably from 0 to about 10, more preferably from 0 to about 3; PA1 wherein R.sup.17 and R.sup.18 comprises C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, and mixtures thereof; PA1 wherein A is the heteroatom nitrogen or oxygen, preferably A is oxygen, the index k is 0 when the heteroatom is absent, k is equal to 1 when the heteroatom is present, Z is hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkyleneamino, --SO.sub.3.sup.- M.sup.+, --OSO.sub.3.sup.- M.sup.+, --CO.sub.2 M, --CH.sub.2 CO.sub.2 M, and mixtures thereof, preferably hydrogen or C.sub.1 -C.sub.30 alkoxy; n is from 1 to 100, preferably from 0 to about 20, more preferably from 2 to about 10; and m is from 1 to 12, preferably from about 1 to about 5; PA1 wherein R.sup.9 comprises: PA1 wherein Z is hydrogen, C.sub.1 -C.sub.30 alkyl, hydroxyl, --CO.sub.2 M, --CH.sub.2 CO.sub.2 M, --SO.sub.3.sup.- M.sup.+, --OSO.sub.3.sup.- M.sup.+, C.sub.1 -C.sub.6 alkoxy, aryl, substituted aryl, aryloxy, substituted aryloxy alkyleneamino; and mixtures thereof; A units comprise nitrogen or oxygen, M is a water soluble cation, k is 0 or 1, n is from 0 to 100, m is from 0 to 12; and mixtures thereof; and, alkyleneamino units and mixtures thereof. PA1 Y is a linking moiety selected from the group consisting of O, CR.sup.25 R.sup.26, OSiR.sup.25 R.sup.26, OSnR.sup.25 R.sup.26, and mixtures thereof; wherein R.sup.25 and R.sup.26 are hydrogen, C.sub.1 -C.sub.4 alkyl, halogen, and mixtures thereof; i is 0 or 1, j is from 1 to 3; PA1 K is a ligand selected from the group consisting of: PA1 Q is an ionic moiety having the formula: EQU --R.sup.24 --W PA1 wherein Z is selected from the group consisting of hydrogen, C.sub.7 -C.sub.20 linear alkyl, C.sub.3 -C.sub.20 branched alkyl, C.sub.2 -C.sub.20 linear alkenyl, C.sub.3 -C.sub.20 branched alkenyl, C.sub.6 -C.sub.10 aryl, C.sub.7 -C.sub.20 arylalkyl, C.sub.7 -C.sub.20 alkylaryl, and mixtures thereof; R.sup.22 is selected from the group consisting of C.sub.1 -C.sub.4 linear alkylene, C.sub.3 -C.sub.4 branched alkylene, and mixtures thereof, R.sup.23 is selected from the group consisting of C.sub.2 -C.sub.6 alkylene, C.sub.3 -C.sub.6 branched alkylene, C.sub.6 -C.sub.10 arylene, and mixtures thereof, x is from 1 to 50, y is 0 or 1. PA1 wherein Y is a linking moiety selected from the group consisting of O, CR.sup.25 R.sup.26 OSiR.sup.25 R.sup.26, OSnR.sup.25 R.sup.26, and mixtures thereof; i is 0 or 1, j is from 1 to 3; Q is an ionic moiety having the formula: EQU --R.sup.24 --W PA1 wherein i is equal to 1 and j is equal to 1. Further examples have the formula ##STR32## PA1 wherein i is equal to 1 and j is equal to 3. The above examples also apply to Y units when used with Q ionic moieties. PA1 a) at least about 0.1%, preferably from about 0.1% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to about 20% by weight, of a detersive surfactant, said detersive surfactant is selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; PA1 b) at least about 0.001 ppm, preferably from about 0.01 to about 10000 ppm, more preferably from about 0.1 to about 5000 ppm, most preferably form about 10 to about 1000 ppm, of a source of singlet oxygen having the formula: PA1 wherein P is a photosensitizing unit; each D is independently a having the formula: EQU --L.sup.1 --R PA1 c) the balance carriers and adjunct ingredients, said adjunct ingredients are members selected from the group consisting of buffers, builders, chelants, filler salts, soil release agents, dispersants, enzymes, enzyme boosters, perfumes, thickeners, abrasives, solvents, clays, and mixtures thereof. PA1 a) at least 0.1% preferably from about 0.1% to about 30%, more preferably from about 1% to about 30% by weight, most preferably from about 5% to about 20% by weight, of a detersive surfactant, said detersive surfactant is selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; PA1 b) at least about 0.001% by weight, of a source of singlet oxygen having the formula PA1 wherein P is a photosensitizing unit; each D is independently a having the formula: PA1 c) the balance carriers and adjunct ingredients, said adjunct ingredients are members selected from the group consisting of buffers, builders, chelants, filler salts, soil release agents, dispersants, enzymes, enzyme boosters, perfumes, thickeners, abrasives, solvents, clays, and mixtures thereof. PA1 wherein m and n are integers of 2 of greater and the sum of m+n is typically about 9 to 17, and M is a water-solublizing cation.
It has been a task of formulators of photobleaches to modify the properties of the (Sens.) unit of the molecule to increase the quantum efficiency without reducing the water solubility. While balancing water solubility and enhanced photophysics, the formulator must insure that the structural modifications do not increase the color.
Surprisingly, it has been found that the compounds of the present invention allow the formulators to increase the photoefficiency of the photoactive compounds without adversely affecting the other parameters of the molecule. This ability to delineate and selectively modify the key structural elements contributing to the target properties of the molecule allows the formulator to proceed without having to rely upon a "hit and miss" stratagem.
The photobleaches of the invention comprise a photosensitizing ring which chelates a photoactive metal or non-metal. To this photoactive metal or non-metal is attached a photo activating ligand which enhances the photoefficiency of the molecule via the "heavy atom effect". In addition to the photoactivating ligand, the photobleaches of the present invention also comprise an axial group which mediates solubility and substantivity of the molecule.
It is therefore an object of the present invention to provide photochemical singlet oxygen generators which serve as photobleaches and photodisinfectants. It is a further object of the present invention to provide photobleaching compositions suitable for use as laundry detergent bleaching compositions.
It is a yet further object of the present invention to provide enhanced photobleaching hard surface cleaning compositions for non-porous hard surfaces, inter alia, Formica.RTM., ceramic tile, glass, or for porous hard surfaces such as concrete or wood.
It is a still further object of the present invention is to provide a method for bleaching fabric with laundry compositions comprising the photobleaching compounds of the present invention.
It is yet still a further object of the present invention is to provide a method for cleaning hard surfaces with the photobleaching compounds of the present invention.